US3849478A - Tetrahydro-1-naphthyl-n-methyl-carbamates - Google Patents
Tetrahydro-1-naphthyl-n-methyl-carbamates Download PDFInfo
- Publication number
- US3849478A US3849478A US00252329A US25232972A US3849478A US 3849478 A US3849478 A US 3849478A US 00252329 A US00252329 A US 00252329A US 25232972 A US25232972 A US 25232972A US 3849478 A US3849478 A US 3849478A
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- US
- United States
- Prior art keywords
- tetrahydro
- naphthyl
- methylcarbamate
- test
- plants
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C37/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring
- C07C37/62—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/22—O-Aryl or S-Aryl esters thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/40—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings
- C07C271/42—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/44—Esters of carbamic acids having oxygen atoms of carbamate groups bound to carbon atoms of six-membered aromatic rings with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/16—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton
- C07C317/22—Sulfones; Sulfoxides having sulfone or sulfoxide groups and singly-bound oxygen atoms bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/02—Systems containing two condensed rings the rings having only two atoms in common
- C07C2602/04—One of the condensed rings being a six-membered aromatic ring
- C07C2602/10—One of the condensed rings being a six-membered aromatic ring the other ring being six-membered, e.g. tetraline
Definitions
- This invention relates to methods and compositions for combating insects.
- this invention relates to certain specifically substituted 5,6,7,8-tetrahydro-l-naphthyl methylcarbamate compositions which are novel per se.
- the compounds which are employed as the active ingredients in the pesticidal compositions of this invention are 4 substituted-5,6,7,8-tetrahydro-l-naphthyl methylcarbamate compounds corresponding to the following general formula:
- Aromatic substituents may be substituted with any essen- United States Patent (3 tially inert substituents such as halogen, nitro, lower alkyl, lower alkoxy, lower haloalkyl or aralkoxy groups.
- novel compositions of this invention are those conforming to the following generic formula:
- N A--NR' lower alkylureido: NHOO--NHR dilower alkylureido: NHCO--NR lower alkoxy: OR lower aralkoxy: -O-A-A lower alkylthio: SR' lower aralkylthio: -SA--A, lower alkyl sulfinyl: SOR' lower alkyl sulfonyl: SO -R' halogen: C1, -Br, --F nitro: NO
- R is lower alkyl
- A is lower alkylene and A, is a substituted or unsubstituted monocyclic hydrocarbon ring.
- Aromatic substituents may be substituted with any essentially inert substituents such as halogen, nitro, lower alkyl, lower alkcxy, lower haloalkyl or aralkoxy groups.
- compositions of this invention are the following:
- the composition where R is amino is prepared by hydrolyzing an alkylideneimino derivative.
- the lower alkylamino derivatives are prepared by hydrogenation of the corresponding alkylideneimino derivative.
- the alkylideneimino naphthol precursor is prepared by reacting 4- aminonaphthol with an appropriate aldehyde.
- the 4-acylamido and 4-arylcarboxamido naphthols are prepared by the reaction of the appropriate acid halide or anhydride with 4-aminonaphthol.
- the alkyl ureido derivatives are prepared by reacting 4-aminonaphthol with methyliso cyanate simultaneously producing the carbamate.
- the dialkyl ureido naphthols are prepared by reacting dimethyl carbamoyl chloride with 4-aminonaphthol.
- the alkyl sulfinyl and alkyl sulfonyl substituted compounds are prepared by oxidation of the corresponding lower alkyl thionaphthylcarbamate compound.
- the conversion of the l-naphthol composition to the corresponding n-methylcarbamate is preferably conducted in an inert solvent at ambient temperature but can be carried out at temperatures of from to 100 C.
- a suitable catalyst such as 1,4-diazadicyclo(2.2.2-octane), trimethylamine, triethylamine or dibutyltin diacetate, although in some instances no catalyst is required.
- reaction mixture was poured into two liters of iced water. A light brown solid precipitated and was collected by filtration. After washing thoroughly with water and drying, the solid melted at 150. Recrystallization from ethanol raised the melting point to 159-160". Further recrystallization from xylene increased it to 167-168. The yield was 40 g.
- a series of compounds representative of the compounds useful according to our invention were evaluated for pesticidal activity.
- the compounds were evaluated with respect to their contact and systemic activity against respective insects, viz., two spotted spider, mite, bean, aphid, southern armyworm, Mexican bean beetle, and house fly, by the following standard procedures.
- Suspensions of the test compounds were prepared by dissolving one gram of compound in 50 milliliters of acetone in which had been dissolved 0.1 gram (10 percent of the weight of compound) of an alkylphenoxy polyethoxyethanol surfactant, as an emulsifying or dispersing agent. The resulting solution was mixed into milliliters of water to give roughly 200 milliliters of a suspension containing the compound in finely divided form. The thusprepared stock suspension contained 0.5 percent by weight of compound. The test concentrations employed in the tests described hereinbelow was obtained by diluting the stock suspension with water. Serial dilution tests were carried out in the indicated instances to determine the LD (concentration of chemical required to kill fifty percent of the insect population) values for each test compound. The test procedures were as follows:
- Bean Aphid Foliage Spray Test Adults and nymphal stages of the bean aphid (Aphis fabae Scop.), reared on potted dwarf nasturtium plants at 65-70 F. and 50-70 percent relative humidity, constituted the test insects.
- the number of aphids per pot was standardized to 100-150 by trim ming plants containing excess aphids.
- the test compounds were formulated by diluting the stock suspension with water to give a suspension containing 100 parts of test compound per million parts of final formulation, by weight.
- the potted plants (one pot per compound tested), infested with 100-150 aphids, were placed on a revolving turntable and sprayed with 100-110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at p.s.i.g. air pressure. This application, which lasted 30 seconds, was suflicient to wet the plants to run-off.
- 100-110 milliliters of water-acetone-emulsifier solution containing no test compound were also sprayed on infested plants. After spraying, the pots were placed on their sides on a sheet of white standard mimeograph paper which had been previously ruled to facilitate counting.
- Southern Armyworm Leaf Dip Test Larvae of the southern armyworm (Prodenia eridania (Cram.)), reared on Tendergreen bean plants at a temperature of 80:5 F. and a relative humidity of 50:5 percent, constituted the test insects.
- the test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation (by Weight). Paired seed leaves, excised from Tendergreen bean plants, were dipped in the test formulations until thoroughly Wetted, excess liquid being removed by gentle shaking. While the leaves were drying in a ventilated hood, wilting was prevented by placing the stems in water.
- the paired leaves When dry, the paired leaves were separated and each one was placed in a 9-centimeter Petri dish lined with moistened filter paper. Five randomly selected larvae were introduced into each dish and the dishes were closed. The closed dishes were labeled and held at 80-85 F. for three days. Although the larvae could easily consume the whole leaf within twenty-four hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation by prodding, were considered dead. Percent mortality was recorded for various concentration levels.
- Mexican Bean Beetle Leaf Dip Test Third instar larvae of the Mexican bean beetle (Epilachna varz'vestis Muls.), reared on Tendergreen bean plants at a temperature of 80:5 F. and 50:5 percent relative humidity, were the test insects.
- the test compounds were formulated by diluting the stock suspension with water to give a suspension containing 100 parts of test compound per million parts of final formulation by weight. Paired seed leaves excised from Tendergreen bean plants were dipped in the test formulation until thoroughly wetted, excess liquid being removed by gentle shaking. While the leaves were drying under a hood, wilting was prevented by placing the stems in water.
- the paired leaves When dry, the paired leaves were separated and each was placed in a 9-centimeter Petri dish lined with moistened filter paper. Four randomly selected larvae were introduced into each dish, and the dishes were closed. The closed dishes were labeled and held at a temperature of :5 F. for three days. Although the larvae could easily consume the leaf within 24 to 48 hours, no more food was added. Larvae which were unable to move the length of the body, even upon stimulation, were considered dead. Percent mortality was recorded for various concentration levels.
- test compounds were formulated by diluting the stock suspension with a 10 percent (by weight) sugar solution to give a suspension containing 500 parts of test compound per million parts of final formulation, by weight.
- Ten milliliters of the test formulation were added to a soufll cup containing a oneinch square of an absorbent pad. This bait cup was introduced and centered on the blotting paper under the food strainer prior to admitting the flies.
- the caged flies were allowed to feed on the bait for twenty-four hours, at a temperature of 80:5 F. and the relative humidity of 50:5 percent. Flies which showed no sign of movement on prodding were considered dead. Percent mortality was recorded for various concentration levels.
- Mite Ovicide Test The test organism was the egg of the two-spotted mite (Tetranychus Urticae Koch), as obtained from adults reared on Tendergreen bean plants under controlled conditions of 80:5 F. and 50:5 percent relative humidity. Heavily infested leaves from a stock culture were placed on the primary leaves of two bean plants six to eight inches in height, growing in a two-and-a-half inch clay pot. Females were allowed to oviposit for a period of 48 hours and then the leaves of the infested plants were dipped in a solution containing 800 parts of tetraethyl pyrophosphate per million parts of water in order to destroy the reproductory forms and thus prevent further egg laying.
- mite Tetranychus Urticae Koch
- This solution of tetraethyl pyrophosphate does not affect the viability of the eggs.
- the plants were allowed to dry thoroughly.
- the test compounds were formulated by diluting the stock suspension with water to give a suspension containing 500 parts of test compound per million parts of final formulation.
- the potted plants (one pot per compound) were placed on a revolving turntable and sprayed with -110 milliliters of test compound formulation by use of a DeVilbiss spray gun set at 40 p.s.i.g. air pressure. This application, which lasted 30 seconds, was suflicient to wet the plants to run-01f.
- insect species employed in the above tests are merely representative of a wide variety of pests that can be controlled by use of our compounds.
- the hornworm, cabbage worm, corn ear worm, and Colorado potato beetle can also be combated with our compounds.
- Pesticidal compositions containing the compounds as the active toxicant will usually comprise a carrier and/or diluent, either liquid or solid.
- Suitable liquid diluents or carriers include water, petroleum distillates, or other liquid carriers with or without surface active agents.
- Liquid concentrates may be prepared by dissolving one of these compounds with a nonphytotoxic solvent such as acetone, xylene, or nitrobenzene and dispersing the toxicants in water with the aid of suitable surface active emulsifying and dispersing agents.
- dispersing and emulsifying agents and the amount employed is dictated by the nature of the composition and the ability of the agent to facilitate the dispersion of the toxicant. Generally, it is desirable to use as little of the agent as is possible, consistent with the desired dispersion of the toxicant in the spray so that rain does not re-emulsify the toxicant after it is applied to the plant and wash it off the plant.
- Nonionic, anionic, or cationic dispersing and emulsifying agents may be employed, for example, the condensation products of alkylene oxides with phenol and organic acids, alkyl aryl sulfonates, complex ether alcohols, quaternary ammonium compounds, and the like.
- the active ingredient is dispersed in and on an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like.
- an appropriately divided solid carrier such as clay, talc, bentonite, diatomaceous earth, fullers earth, and the like.
- the aforementioned dispersing agents as well as lignosulfonates can be included.
- the required amount of the toxicants contemplated herein may be applied per acre treated in from 1 to 200 gallons or more of liquid carrier and/or diluent or in from about 5 to 500 pounds of inert solid carrier and/or diluent.
- concentration in the liquid concentrate will usually vary from about 10 to 95 percent by weight and in the solid formulations from about 0.5 to about percent by weight. Satisfactory sprays, dusts, or granules for general use contain from about A to 15 pounds of active toxicant per acre.
- the pesticides contemplated herein prevent attack by insects upon plants or other material to which the pesticides are applied, and they have high residual toxicity. With respect to plants they have a high margin of safety in that when used in sufiicient amount to kill or repel the insects, they do not burn or injure the plant, and they resist weathering which includes wash-oft" caused by rain, decomposition by ultra-violet light, oxidation, or hydrolysis in the presence of moisture or, at least, such decomposition, oxidation, and hydrolysis as would materially decrease the desirable insecticidal characteristic of the toxicants or impart undesirable characteristics, for instance, phytotoxicity, to the toxicants.
- the toxicants are so chemically inert that they are now compatible with substantially any other constituents of the spray schedule, and they may be used in the soil, upon the seeds, or the roots of plants without injuring either the seeds or roots of plants, yet by root uptake they will 'kill the pests feeding thereon.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
1-(H3C-NH-COO-),4-R1-5,6,7,8-TETRAHYDRONAPHTHALENE
WHEREIN R1 IS FORMAMIDO, LOWER ALKANOYLAMIDO, PHENYLCARBOXAMIDO LOWER ALKYLIDENEIMINO, DILOWER ALKYLAMINO LOWER ALKYLENEIMINO, LOWER ALKYLUREIDO, DILOWER ALKYLUREIDO, LOWER PHENYLALKOXY, LOWER ALKYLTHIO, LOWER PHENYLALKYLTHIO, LOWER ALKYL SULFINYL OR LOWER ALKYL SULFONYL.
Description
Claims (1)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00252329A US3849478A (en) | 1972-05-10 | 1972-05-10 | Tetrahydro-1-naphthyl-n-methyl-carbamates |
US05/448,699 US3958006A (en) | 1972-05-10 | 1974-03-06 | Carbamate pesticidal compositions |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US00252329A US3849478A (en) | 1972-05-10 | 1972-05-10 | Tetrahydro-1-naphthyl-n-methyl-carbamates |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US05/448,699 Division US3958006A (en) | 1972-05-10 | 1974-03-06 | Carbamate pesticidal compositions |
Publications (1)
Publication Number | Publication Date |
---|---|
US3849478A true US3849478A (en) | 1974-11-19 |
Family
ID=22955569
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US00252329A Expired - Lifetime US3849478A (en) | 1972-05-10 | 1972-05-10 | Tetrahydro-1-naphthyl-n-methyl-carbamates |
Country Status (1)
Country | Link |
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US (1) | US3849478A (en) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5534653A (en) * | 1993-11-11 | 1996-07-09 | Basf Aktiengesellschaft | P-hydroxyaniline derivatives, their preparation and their use |
US5565490A (en) * | 1993-11-11 | 1996-10-15 | Basf Aktiengesellschaft | P-hydroxyaniline derivatives, their preparation and their use |
-
1972
- 1972-05-10 US US00252329A patent/US3849478A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5534653A (en) * | 1993-11-11 | 1996-07-09 | Basf Aktiengesellschaft | P-hydroxyaniline derivatives, their preparation and their use |
US5565490A (en) * | 1993-11-11 | 1996-10-15 | Basf Aktiengesellschaft | P-hydroxyaniline derivatives, their preparation and their use |
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Date | Code | Title | Description |
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AS | Assignment |
Owner name: MORGAN GUARANTY TRUST COMPANY OF NEW YORK, AND MOR Free format text: MORTGAGE;ASSIGNORS:UNION CARBIDE CORPORATION, A CORP.,;STP CORPORATION, A CORP. OF DE.,;UNION CARBIDE AGRICULTURAL PRODUCTS CO., INC., A CORP. OF PA.,;AND OTHERS;REEL/FRAME:004547/0001 Effective date: 19860106 |
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AS | Assignment |
Owner name: UNION CARBIDE CORPORATION, Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:MORGAN BANK (DELAWARE) AS COLLATERAL AGENT;REEL/FRAME:004665/0131 Effective date: 19860925 |
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Owner name: UNION CARBIDE AGRICULTURAL PRODUCTS COMPANY, INC., Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNION CARBIDE CORPORATION A CORP. OF NY;REEL/FRAME:004748/0190 Effective date: 19860930 |
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Owner name: UNION CARBIDE CORPORATION, 39 OLD RIDGEBURY RD., D Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNION CARBIDE AGRICULTURAL PRODUCTS COMPANY, INC., A CORP. OF PA;REEL/FRAME:004761/0647 Effective date: 19861218 Owner name: UNION CARBIDE CORPORATION,CONNECTICUT Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:UNION CARBIDE AGRICULTURAL PRODUCTS COMPANY, INC., A CORP. OF PA;REEL/FRAME:004761/0647 Effective date: 19861218 |
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Owner name: RHONE POULENC NEDERLANDS B.V., DRAAISTROOM 1, POST Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:UNION CARBIDE CORPORATION;REEL/FRAME:004751/0394 Effective date: 19861219 |